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Publication numberUS7537789 B1
Publication typeGrant
Application numberUS 11/182,275
Publication dateMay 26, 2009
Filing dateJul 15, 2005
Priority dateJul 15, 2005
Fee statusPaid
Publication number11182275, 182275, US 7537789 B1, US 7537789B1, US-B1-7537789, US7537789 B1, US7537789B1
InventorsJoe D. Henry, John R. Hardee, E. Field Selby
Original AssigneeEnvirovest Llc
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
System controlling soluble phosphorus and nitrates and other nutrients, and a method of using the system
US 7537789 B1
Abstract
The invention includes an alkali metal silicate based solution that, either alone or following an alkali earth metal salt activator, binds soluble phosphorus and/or nitrates.
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Claims(1)
1. A composition for treating animal waste having naturally excessive amounts of phosphorus or nitrates, said composition comprising an aqueous alkali metal silicate comprising aqueous sodium silicate at a concentration in the range of about 20% by weight, an anionic surfactant comprising an ester of organo-phosphoric acid comprising a concentration range of about 1% by weight, and a polyol comprising propylene glycol comprising a concentration range of about 1% by weight, said composition chemically binding soluble phosphorus into a stable complex, said binding composition able to bind up to 50% of such soluble phosphorus.
Description
CROSS REFERENCE TO RELATED APPLICATIONS

Not applicable.

FEDERALLY SPONSORED RESEARCH AND DEVELOPMENT

Not applicable.

MICROFICHE APPENDIX

Not applicable.

BACKGROUND OF THE INVENTION

(1) Field of the Invention

The present invention generally relates to systems of chemicals and solutions for controlling substances that are nutrients for plants and microorganisms when available in optimal amounts, but which are considered contaminants when available in overabundance. Such control may optimize the use of abundant animal waste as fertilizers, without adversely affecting surface water. More preferably, the present invention involves solutions that bind soluble phosphorus and nitrates commonly found in animal waste and fertilizers (and the soil upon which those are spread), rendering them unavailable for leaching into adjacent soil or water. Moreover, the present invention relates to treatments for soil including chicken litter or other animal waste. The present invention also includes methods of using said solutions, and methods of using the combination of said solution(s) and animal waste treated therewith to provide a fertilizer or soil addendum.

This invention relates to a system for controlling the availability of plant nutrients and perhaps other growth factors, together with the method of using the contaminant remedial composition. Contamination of soil and water, by pollutants or even by an overabundance of otherwise neutral or beneficial substances, are serious environmental concerns at this time. Great concern has been expressed for decades over the accumulation and disposal of wastes, especially those accumulating during the mass-production of poultry, cattle, swine and other animals. Substances commonly found or accumulating in soil and water include soluble phosphorus, nitrates, arsenic and selenium. Moreover, although most of those substances are considered to be beneficial plant nutrients (or growth factors for microorganisms) when present in optimal quantities, overabundance may result in over-growth of plants and microorganisms that can themselves harm soil (or nearby surface water).

In one typical scenario, chicken litter in poultry houses accumulates with an overabundance of moisture, ammonia, dust and microbes, adversely affecting animal health. That chicken litter often is removed and used as fertilizer, because of its high content of plant nutrients. Constituents such as soluble phosphorus and nitrates often leach into surface waters and spawn aquatic overgrowth, causing environmental problems such as eutrophication of water sources. The present invention both optimizes the availability of plant nutrients for crop growth and reduces (or prevents) the growth of algae and other plants associated with eutrophication.

(2) Description of Related Art Including Information Disclosed 37 CFR 1.97 and 1.98

Known in the art are various pollution remedial compositions. For example, the following patents and unpatented products are arguably related to the patentability of the subject invention:

U.S. Pat. No. 5,478,389 issued to Loomis discloses a pollution remedial composition comprising a soluble silicate (preferably sodium silicate), a surfactant, a polyol and water. The Loomis composition may also include sodium chloride and citric acid, and possibly glycerine. Loomis does not disclose the application of any such composition to animal waste or any other substance or substratum containing an overabundance of phosphorus, nitrates, moisture, ammonia, arsenic, selenium, dust particles or microbes, nor is any such application inherent in Loomis.

Some known products such as Alum and AlClear are known to use aluminum sulfate to reduce ammonia and/or soluble phosphorus in chicken litter. However, an excessive level of aluminum sulfate is harmful to soil and animal health. Another such product, PLT, reduces ammonia in chicken litter, but has been shown to be corrosive to metals.

BRIEF SUMMARY OF THE INVENTION

One general version of the present invention comprises (includes) a solution for spraying on substrate contaminated with soluble phosphorus and/or nitrates (such as chicken litter), to bind such ortho-phosphate and prevent it from later becoming re-dissolved. Although the invention has several embodiments, one basic embodiment also includes an activator for applying to the contaminated substrate, then spraying an aqueous solution of alkali metal silicate for immobilizing the migration of soluble phosphorus.

In a more detailed version of the invention, before being applied to the phosphorus-contaminated substrate, an aqueous solution of the following is prepared: an alkali metal silicate; an anionic surfactant such as an ester of organo-phosphoric acid; and a polyol such as polypropylene glycol. An alkaline earth metal salt based activator may be applied to the substrate before application of that aqueous solution. Such compounds include calcium acetate, magnesium nitrates or barium chloride.

It is believed that the process involves conversion of soluble phosphorus, resulting in the chelating of phosphorus for the formation of an inert dehydrated phospho-silicate apatite. The silicate is believed to be a binding agent, for binding metal cations in a stable complex. When metal cations such as alkaline earth cations exchange with alkali metal cations, a charge imbalance is created in the silicate complex with the result that phosphorus is incorporated in the complex and rendered unavailable for further reaction with other reagents.

One primary object of the present invention is to provide a new and effective composition for controlling the availability of plant nutrients in soil, together with a method of using the composition.

Another primary object of the present invention is to provide a composition for adding growth factors to soil, such as a fertilizer or soil amendment, together with a method of using same.

It is another object of the present invention to provide a composition that can effectively reduce the soluble phosphorus content of chicken litter and other animal waste, or the soil upon which such waste is situated.

It is another object of the present invention to provide a composition that can effectively reduce the soluble nitrate content of chicken litter and other animal waste, or the soil upon which such waste is situated.

It is yet another object of the present invention to provide a composition that can effectively reduce the arsenic content of chicken litter and other animal waste, or the soil upon which such waste is situated.

It is also an object of the present invention to provide a composition that can effectively reduce the selenium content of chicken litter and other animal waste, or the soil upon which such waste is situated.

It is another object of the present invention to provide a composition that can effectively reduce the amount or concentration of moisture, airborne dust and microbes in animal confines such as poultry houses, feed lots and other areas of animal concentration.

It is still another object of the present invention to provide a composition that can effectively reduce the ammonia concentrations in animal confines such as poultry houses, feed lots and other areas of animal concentration.

Other objects will be apparent from a reading of the written description disclosed herein, together with the claims.

BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS

FIG. 1 is a table showing the percentage of σ-P removal from aqueous solution, in Example 1.

FIG. 2 is a table showing σ-P removal from litter treatment, in Example 1.

FIG. 3 is a table showing σ-P removal from a second litter treatment, in Example 1.

FIG. 4 is a table showing σ-P removal from a third litter treatment using the Mehlich III Extraction Procedure, in Example 1.

FIG. 5 is a comparison of 10% activator and SB for binding phosphorus and nitrate, in Example 2.

FIG. 6 is a comparison of 5% activator and SB for binding phosphorus and nitrate, in Example 2.

FIG. 7 is a graph depicting changes in nitrate concentration of chicken litter when treated with test solutions, in Example 2.

FIG. 8 is a graph depicting changes in phosphorus concentration of chicken litter when treated with test solutions, in Example 2.

These drawings illustrate certain details of certain embodiments. However, the invention disclosed herein is not limited to only the embodiments so illustrated. The invention disclosed herein may have equally effective or legally equivalent embodiments.

DETAILED DESCRIPTION OF THE INVENTION

For the sake of simplicity and to give the claims of this patent application the broadest interpretation and construction possible, the following definitions will apply:

The term “plant nutrient” or derivative thereof essentially means phosphorus and nitrates in a form acceptable to plant metabolism.

The term “growth factor” or derivative thereof essentially means the plant nutrients (soluble phosphorus and nitrates), arsenic and/or selenium.

Also for the sake of simplicity, the conjunctive “and” may also be taken to include the disjunctive “or,” and vice versa, whenever necessary to give the claims herein the broadest interpretation and construction possible. Likewise, when the plural form is used, it may be taken to include the singular form, and vice versa.

The invention disclosed herein is not limited by ingredients to the extent that such materials satisfy the structural and/or functional requirements of any claim.

Although the invention has a number of features and variations, its most general form includes (comprises) a composition for controlling the availability of plant nutrients in soil, comprising an aqueous alkali metal silicate. Said plant nutrients may be selected from the group consisting of soluble phosphorus and nitrates, and combinations and mixtures thereof. Each of said substances has a common characteristic justifying its inclusion in this group, namely, these otherwise beneficial substances may be present in such high concentrations as to present environmental concerns. One main version of the invention affects the plant nutrient soluble phosphorus.

One general version of the invention is a composition wherein said aqueous alkali metal silicate is selected from the group consisting of sodium silicate and potassium silicate, and combinations and mixtures thereof. Each of said substances has a common characteristic justifying its inclusion is this group, namely, acting as a binding agent for binding metal cations in a stable complex. Said aqueous alkali metal silicate may include aqueous sodium silicate at a concentration in the range of between about 1% and 42% by weight. Alternately, said aqueous alkali metal silicate may be aqueous potassium silicate at a concentration in the range of between about 1% and 42% by weight.

Said soluble phosphorus may include (comprise) solid animal waste and, if so, said availability of plant nutrients may be reduced by up to 50%.

Another version of the invention further includes an activator, greatly enhancing the effectiveness, resulting from unexpected synergies attributable to the presence of said activator. Said plant nutrients may be selected from the group consisting of phosphorus and nitrates, and combinations and mixtures thereof. Said plant nutrient may include soluble phosphorus, and said activator may include an aqueous alkaline earth metal salt. More particularly, said aqueous alkaline earth metal salt may be selected from the group consisting of water soluble alkaline earth metal salts, such as (for example) sulfates, nitrates, chlorides and acetates, and combinations and mixtures thereof. Said soluble alkaline earth metal salt may be magnesium sulfate at a concentration of between about 1% and 20% by weight. Alternatively, said soluble alkaline earth metal salt may be calcium nitrates at a concentration of between about 1% and 20% by weight.

When using one of the above described compositions, and said soluble phosphorus includes solid animal waste, said availability of plant nutrients may be reduced by up to 86%.

Another version of the invention includes a composition described above wherein said plant nutrient is nitrate. When using one of the above described compositions, and said soluble phosphorus and nitrates includes solid animal waste, said availability may be reduced considerably; said soluble phosphorus may be reduced by up to 86%, and said nitrates may be reduced by up to 99%.

Another version of the invention further includes a surfactant and/or a polyol. More particularly, said surfactant may include an anionic surfactant, preferably selected from the group consisting of phosphate esters, and combinations and mixtures thereof. Each of said substances has a common characteristic justifying its inclusion is this group, namely, lowering the surface tension of the aqueous alkali metal silicate solution. Even more particularly, said surfactant may be ester of organo-phosphoric acid, preferably in a concentration range of between about 1% and 5% by weight. Even more particularly, said ester of organo-phosphoric acid may be in a concentration range of about 1% by weight.

Said polyol may be propylene glycol, preferably in a concentration range of about 1% by weight.

Another version of the invention includes a composition for adding growth factors to soil. Besides the aforementioned plant nutrients (phosphorus and nitrates), said growth factors may be selected from the group also consisting of moisture, ammonia, arsenic, selenium, dust particles and microbes, and mixtures and combinations thereof. Each of said substances has a common characteristic justifying its inclusion is this group, namely, substances present in poultry litter or animal waste that, when accumulated or aggregated, is harmful to the environment. This version of the invention essentially manifests additional utility through an independent, secondary use of the above described treatment compositions, as a soil amendment or fertilizer. The present invention is capable of preserving (in the animal waste) enough of the nutrients necessary for plant growth, but reducing concentrations that may produce negative environmental impact. One such version includes a combination of animal waste treated with one of the above described treatment compositions for controlling the availability of said growth factors in said animal waste. More particularly, said treatment composition may include an aqueous alkali metal silicate. Said aqueous alkali metal silicate may be aqueous sodium silicate at a concentration in the range of between about 1% and 42% by weight. Alternatively, said aqueous alkali metal silicate may be aqueous potassium silicate at a concentration in the range of between about 1% and 42% by weight.

Said growth factor may be soluble phosphorus and, if said soluble phosphorus is included in solid animal waste (such as chicken litter, for example), said availability may be reduced by up to 50%.

Another version of this soil addendum version may further include an activator, especially including an aqueous alkaline earth metal salt. Said aqueous alkaline earth metal salt may be selected from the group consisting of water soluble alkaline metal salts such as (for example) sulfates, nitrates, chlorides and acetates, and combinations and mixtures thereof. More particularly, said soluble alkaline earth metal salt may include magnesium sulfate at a concentration of between about 1% and 20% by weight. Alternatively, said soluble alkaline earth metal salt is calcium nitrates at a concentration of between about 1% and 20% by weight. When said soluble phosphorus is included in solid animal waste, said availability is reduced by up to 86%.

Said growth factor may include nitrate. When said soluble phosphorus and nitrates are included in solid animal waste, and said availability may be reduced considerably; said soluble phosphorus may be reduced by up to 86%, and said nitrates may be reduced by up to 99%.

In one particular version of a soil amendment version of the invention, said animal waste comprises chicken litter, said soluble alkaline earth metal salt comprises magnesium sulfate at a concentration of between about 1% and 20% by weight, and said growth factor comprises arsenic. In another particular version of a soil amendment version of the invention, said animal waste comprises turkey litter, said soluble alkaline metal salt comprises calcium acetate at a concentration of between about 1% and 20% by weight, and said growth factor comprises selenium. In yet another particular version of a soil amendment version of the invention, said animal waste comprises hog manure, said soluble alkaline metal salt comprises barium chloride at a concentration of between about 1% and 20% by weight, and said growth factor comprises nitrates.

As with the plant nutrient controlling version of the invention, the soil amendment version may also include a surfactant and/or a polyol; said surfactant may include an anionic surfactant, especially selected from the group consisting of phosphate esters, and combinations and mixtures thereof. Said surfactant may be an ester of organo-phosphoric acid, especially in a concentration range of between about 1% and 5% by weight. More particularly, said ester of organo-phosphoric acid may be in a concentration range of about 1% by weight. Similarly, said polyol may be propylene glycol, especially in a concentration range of about 1% by weight.

Besides the aforementioned compositions, the invention described herein also includes a method of using a composition for controlling the availability of plant nutrients (described above), comprising the steps of applying said composition to a substrate susceptible to exposure to unwanted levels of plant nutrients or growth factors. Alternatively, said method may further include the step of mixing the substratum to optimize uniform contact with the substratum. More particularly, said method may include the initial step of applying an activator to a substrate susceptible to exposure to unwanted levels of plant nutrients or growth factors. Even more particularly, said method may further include the step of allowing the mixed substrate to dry.

The invention disclosed herein may also include a method of using a composition for adding growth factors to soil, comprising the step of adding to soil a combination of animal waste and a treatment composition for controlling the availability of said growth factors in said animal waste, described above.

EXAMPLE 1

It has been shown that a silicate blend (“SB”) binds soluble phosphorus in the presence of SB “Activator”. When the treatment sequence utilizes a natural extract from rice hulls (SB “RF”), a 97% reduction in soluble phosphorus occurs from a concentration of 2500 ppm.

Previous laboratory studies have sought to determine the relative effects of the binding capacity of SB treated litter. Treatability studies have been conducted, designed and implemented with the intent to investigate whether phosphorus in chicken litter could be prevented from leaching once treatments had been performed to chelate phosphorus and thus retard its removal.

Materials and Methods

Initial bench studies were conducted to determine the binding efficiency of SB in aqueous solution. Under these experimental conditions, soluble phosphorus was prepared in concentrations of 2500 ppm and mixed with standard solutions of SB and SB “RF” and tested for soluble phosphorus using the Vanadomolybdophosphoric Acid Method of Analysis.

Evaporation to Dryness Method

The SB and SB “RF” have proven to be extremely effective in removing phosphate from aqueous solution in bench level testing. To test these solutions they were mixed with 100 mL of 2500 ppm P (obtained by the dissolution of KH2PO4) stirred for 5 minutes, and then evaporated to dryness at 50° C. to the resulting precipitate, 100 ml of deionized water were added and stirred overnight. The aqueous portion of the rehydrated precipitate was then analyzed according to the Vanadomolybdophosphoric Acid Method.

SB Activator Method

Another effective method of removing phosphorus using these two solutions involves the addition of SB “Activator” to 100 ml of 2500 ppm P followed by the addition of either “RF” or SB original formula. These solutions were stirred for 5 minutes, left overnight, centrifuged and analyzed for phosphorus.

Results and Discussion

Analysis for phosphorus using the Vanadomolybdophosphoric Acid Method showed 99% phosphorus removal using the Original Formula (SB™) and 100% removal using the rice silicate formula (SB “RF”).

Results of the SB and SB “RF” in a treatment scenario using SB “Activator” were completed without drying. The table of FIG. 1 summarizes these results.

SB “Activator” alone does not reduce the phosphorus concentration. For the “RF” and the SB original formula to be effective for phosphorus removal they must be heated to dryness. In the presence of “Activator”, the heating step is not necessary. A greater amount of “Activator” is needed with the “RF” than with the original formula.

Application of the preceding methodology has been adapted for the treatment of dried chicken litter at the bench level of study and testing to evaluate methods of treatment with respect to phosphorus reduction. The standard treatment protocol relies on litter obtained from a broiler house having been in use for approximately two years.

Test Procedure for Litter Treatment

Portions of the litter are retained to determine the pre-test nutrient content, that is, total P, soluble P (σ-P), and N, K, pH and dry matter:

    • 1) Approximately 50 pounds of litter (equilibrated to room temperature and RH) were blended to a uniform mixture in a Hobart blender for 15 minutes.
    • 2) 300 gm samples were removed from the blended sample and placed into each of 25 (9″×13″) aluminum baking pans.
    • 3) One hundred (100) gm samples (comprised of 4-25 gm sub-samples blended for three minutes) were then removed from each pan using clean plastic utensils, and placed into corresponding zip-lock bags and labeled. Four (4) sub-samples are collected for pre-test evaluation.
    • 4) Five (5) pans were randomly treated with the following application:
      • a. A stock SB “Activator” solution was prepared.
      • b. 300 ml quantities of a 5% stock solution were spray applied to each of five (5) pans of litter, while hand mixing. The mixture is allowed to sit at room temperature until ready for SB application.
      • a. 30 & 50 ml of undiluted SB were spray applied to the litter/“Activator” mixture, with hand mixing, until all SB has been added.
      • b. 30 & 50 ml portions of an undiluted formulation using SB “RF” were spray applied to the litter/“Activator” mixture, with hand mixing, until completely blended.
    • 5) A second set of five (5) pans were treated similarly with SB as in step 4 and a third set of five (5) pans are treated with distilled water only.
    • 6) The samples were then placed at elated temperature (˜122° F./35-45% RH), uncovered to effect drying. The samples are allowed to cure* for 18-48 hours or until dry, prior to testing.
    • 7) At the end of the drying cycle, the samples were removed in 2-100 gm* quantities and placed in plastic, zip-lock bags, labeled, and transported to the laboratory for testing. *Eight (8) twenty-five gram samples were removed from eight different locations in the sample mixture and blended for uniformity. The samples were subdivided into 2-100 gram samples.
    • 8) Samples were tested for total P, soluble P (σ-P), and pH. Chain-of-custody forms accompany each sample batch.

A second litter treatment was conducted with samples treated to replicate the treatment procedure tabulated in FIG. 2. Since the SB™ “RF” indicated a higher P removal, the treatment was conducted using “RF” and the SB™ “Activator”. The results are recorded in FIG. 3.

Test Results from Mehlich III Extraction Procedure

The Mehlich extraction procedure is an aggressive extraction procedure that measures the relative bioavailability of σ-phosphorus on acid to neutral pH soils. The test is shown to be correlated to crop response to fertilizer phosphorus. In this case, the total resident to-phosphorus loading is quantified (FIG. 4).

In the analysis, it was shown that even with this aggressive leachate procedure, 74.1% of the phosphorus remains bound and therefore not subject to runoff. If the earlier, conventional method of extraction is compared to the Mehlich II procedure, only a difference of 0.057% separates the two methods.

Conclusions

This preliminary study has been conducted under secured laboratory conditions and the results contained herein culminate bench trials designed to demonstrate the efficacy of treating soluble phosphorus solutions with environmentally non-toxic additives. The ultimate goal is to achieve total phosphorus binding in chicken animal litter destined for land application and thus remove the threat of leaching and runoff into surface waters.

Based on the data generated from these preliminary trials, the binding of soluble phosphorus in aqueous solution has been achieved by the use of both SB and SB “RF” formulations. The binding effects are enhanced by total evaporation to dryness at 50° C. Dryness renders silicates nearly insoluble and with their propensity for cationic exchange, reaction with other materials, such as magnesium or calcium compounds, will make the film coating completely insoluble.

The reaction has been found to be enhanced by the addition of another proprietary solution, SB “Activator”. It has been found that the combination of the two products in the presence of phosphate will bind 97% of the phosphorus in aqueous solution. Similarly, preliminary bench tests to determine the effectiveness of the SB “RF” in reducing soluble phosphorus in chicken litter has produced a mean (x) 74.7% reduction using a 1:1:0.2 litter, Activator, SB mixture. The most recent test cycle (Dec. 14, 2004) establishes the tenacity of the binding process through the Mehlich III extraction procedure and confirms the repeatability and relative ease of treatment.

EXAMPLE 2

The question of whether soluble phosphorus and nitrate binding occurs during the treatment process has been addressed. A series of bench studies have been conducted to determine the binding effects of SB “Activator” formula when applied to chicken litter obtained in de-caking from brooder houses. Variables were introduced to further determine the optimal range for binding phosphorus while maintaining the nutritional demands for nitrate fertilization.

Materials and Methods

Multiple samples of chicken litter were treated initially with 5% solutions of Activator at ratios of 1:1 and 1:0.5, respectively. Added variables included the application of 10% solutions of Activator followed by the addition of SB at 20% concentration in the same treatment sequence ratio.

FIG. 5 illustrates the binding effects of SB and Activator in ratios of 0.5:0.2:1 (Activator:SB:litter) with 10% Activator solution.

The data in FIG. 6 illustrates the optimal effect of phosphorus binding and ready availability of nitrate using a 5% Activator solution at a ratio of 1:0.2:1 (Activator:SB:litter).

FIG. 7 below shows the effect on nitrate reduction of varying volumes of SB (ml of SB per 100 g of chicken litter) using a ratio of 1:1 Activator per 100 gm of chicken litter. There is an inherent flexibility using SB. Varying levels of nitrate reduction can be obtained by adjusting the volume of SB. When a 0.2:1 ratio of SB:chicken litter is used, nitrates are not significantly affected and, therefore, are still available when used as a fertilizer.

The graph in FIG. 7 further illustrates that with increasing volumes of SB, nitrate reduction is proportionately increased but when compared to the effects of increased SB, the binding effects of phosphorus are diminished as shown in FIG. 8. The net effect of the appropriate application rates combine to provide excellent phosphorus reduction but allowing for no net reduction in nitrate.

The phenomenon of reduced SB gives the best results for phosphorus reduction. It is believed that larger quantities of applied SB lead to extensive polymerization that exclude phosphate rather than incorporate it into the polymer.

CONCLUSIONS

Based on the data generated from the experimental procedures for treating chicken litter using SB and Activator, it is concluded that the optimum concentration of Activator is a 5% solution applied at a ratio of 1:1. Whereas, the optimum concentration of SB is a 0.2:1 ratio SB:litter. These ratios and concentrations provide an 86% reduction in soluble phosphorus while maintaining levels of nitrate virtually intact.

The combination and use of various ratios of SB and Activator now demonstrates, at the laboratory level, the flexibility to treat chicken litter for soluble phosphorus reduction, nitrate reduction, and or both, depending on the needs of regional fertilizer applications, or the necessity to treat in favor of phosphorus reduction. This treatment capability will be to the benefit of the environment, while preserving the nutrients needed by the agricultural community, as required.

Those skilled in the art who have the benefit of this disclosure will appreciate that it may be used as the creative basis for designing devices or methods similar to those disclosed herein, or to design improvements to the invention disclosed herein; such new or improved creations should be recognized as dependant upon the invention disclosed herein, to the extent of such reliance upon this disclosure.

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Classifications
U.S. Classification424/722, 424/724
International ClassificationA01N59/26
Cooperative ClassificationC05F3/00
European ClassificationC05F3/00
Legal Events
DateCodeEventDescription
Apr 15, 2014ASAssignment
Owner name: ENVIROVEST LLC (C/O ROLAND GUNN), VIRGINIA
Effective date: 20140401
Owner name: SELBY, E FIELD, CALIFORNIA
Free format text: RELEASE OF LIEN;ASSIGNOR:CALHOUN LAW FIRM;REEL/FRAME:032693/0733
Owner name: HENRY, JOE, ARKANSAS
Owner name: HARDEE, JOHN, ARKANSAS
Oct 23, 2012FPAYFee payment
Year of fee payment: 4
Sep 30, 2009ASAssignment
Owner name: JOE D. CALHOUN LTD D/B/A CALHOUN LAW FIRM, ARKANSA
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Mar 24, 2009ASAssignment
Owner name: JOE D. CALHOUN LTD. D/B/A CALHOUN LAW FIRM, ARKANS
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Aug 15, 2006ASAssignment
Owner name: ENVIROVEST LLC, ARKANSAS
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